We show that solar γ-ray observations can provide a complementary probe of Dark Matter in scenarios where the interactions with the Standard Model proceed via long-lived mediators. For illustration we consider a simplified model which provides solar γ-ray fluxes observable with the next generation γ-ray telescopes, while complying with the existing experimental constraints. Our results suggest that solar γ-ray fluxes can be orders of magnitude larger than the ones from the Galactic center, while being subject to low backgrounds.